Electron Spin Resonance Study of the Photolysis of Polystyrene and Poly(α-Methylstyrene)

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Abstract
The photolysis of polystyrene and poly (α-methylstyrene) was studied by ESR techniques using highly concentrated glassy solutions of the polymers near liquid-nitrogen temperature. Every attempt was made to insure detection of the earliest free-radical species. The use of poly (1-vinylnaphthalene) and polystyrene-2,3,4,5,6-d5 verified that the primary radical species is located on the polymer chain and not the ring. The ESR spectra obtained for both polystyrene and poly (α-methylstyrene) are consistent with the structure HH–C–Ċ–C–HφH. Interpretation of the observed spectra is made on the basis of the stereochemistry of the polymer chain.